Method of preparing aqueous chlorine dioxide solutions

ABSTRACT

The description relates to a process for the production of aqueous chlorine dioxide solutions through oxidation of chlorite with oxo acids and/or oxo acid anions having a suitable redox potential in a buffered aqueous medium, wherein an acidic aqueous solution A is produced which has a pH of about 5 or less and contains the oxo acids and/or oxo acid anions, and the acidic aqueous solution A is mixed with an aqueous chlorite solution B to form chlorine dioxide, wherein a pH of less than 6.95 is adjusted in the reaction mixture, this pH value being stabilized by a buffering system contained therein.

This application is a 371 of PCT/EP96 filed Aug. 9, 1996.

BACKGROUND OF THE INVENTION

a) Field of the Invention

The invention is directed to a process for the production of aqueouschlorine dioxide solutions through oxidation of chlorite with oxo acidsand/or oxo acid anions having a suitable redox potential in a bufferedaqueous medium.

b) Description of the Related Art

Numerous attempts have been made up to the present, without satisfactoryresults, to kill Legionella in hot water systems in order to reducepotential health risks. Further, conditions exist in industrial coldwater systems which favor bacterial growth and which lead to a biofilmon the surfaces of transporting lines which has been countered up to thepresent by biostatic means. For example, isothiazolone, thiocyanates,quaternary ammonium compounds and chlorine-containing compounds are usedfor this purpose. A great disadvantage of these biostatic means consistsin that the cold water often has CSB/BSB values above the limitingvalues due to the large amounts used. In fact, only an increase intemperature to about 73° C. and an increase in the flow volume haveproven suitable for killing Legionella in water systems. However, thereis a risk that after a certain period of time the Legionella which havenot been killed will propagate again from the biofilm and encrusteddeposits in the water line system, especially from so-called deadstrains, and will once again cause lasting contamination of the system.Therefore, nonionic phosphonic acids with hydrogen peroxide (EP 0 540772 A1) or grapefruit seed extract (EO 0 602 891 A1) were recentlyproposed for combatting Legionella. However, none of these methods hasbeen successful.

Aqueous chlorine dioxide solutions are promising candidates for theareas of application mentioned above. However, the known processes forindustrial production of aqueous chlorine dioxide solutions have gravedisadvantages which pose obstacles to the use of chlorine dioxidesolutions produced by these methods in drinking water and in relatedareas.

According to the process in DE-PS 27 28 170, 7 to 21 parts by weight ofchlorite, 7.5 to 22.5 parts by weight of hypochlorite and 0.5 to 1.5parts by weight carbonate are dissolved, in that order, in 35 to 105parts by weight water. In order to adjust a slightly alkaline pH, 7.5 to22.5 parts by weight of diluted inorganic or organic acid are added. Astabilizer, especially in the form of a peroxide, is advantageouslymixed in beforehand.

According to DE-AS 27 30 883, an aqueous chlorine dioxide solution isproduced by acidifying a chorite solution to a pH of about 4 andsubsequently raising the pH value to about 7.0 to 7.2 by adding awater-soluble metal hydroxide. This is followed by the addition ofcarbonate. The teaching disclosed in DE-AS 27 30 883 offers theadvantage that the aqueous chlorine dioxide solution remains stableexclusively through the sodium carbonate, so that additional stabilizersin the form of peroxides, for example, can be dispensed with. Thestabilized chlorine dioxide solution is said to be storable for longperiods of time, that is, months and years, and is suitable particularlyfor treatment of drinking water.

According to the teaching of the two processes mentioned above, thecarbonate serves to ensure buffering in the basic pH range. However, theincorporation of the carbonate stabilizing in the alkaline range leadsto a high pH value which is undesirable for various reasons: a high pHpromotes the reformation of chlorite ions so that the known chlorinedioxide solutions always contain an unwanted proportion of chloriteions. Moreover, in the alkaline range, highly toxic and thereforeundesirable chlorate can form through various types of reactions. Forexample, when alkaline hypochlorite solution is mixed with chloritesolution, the oxidation of the chlorite beyond the oxidation stage ofthe chlorine dioxide leads to chlorate. Further, chlorine dioxide tendsin the alkaline range toward disproportionation in chlorate and theby-product chlorite.

The process according to DE-PS 34 03 631 is also directed to theproduction of a slightly alkaline system based on a chlorite solution.It aims at the production of an aqueous "chlorite" solution which isstabilized by a peroxide compound, modified, and adjusted in thealkaline range. In this process, an aqueous solution with a pH of 3 orless containing sulfate ions is mixed with a peroxide compound which isstable therein, wherein a 0.001 to 0.1 molar concentration of peroxidecompound results in the end product. This solution is mixed with anaqueous alkaline chlorite solution in such quantity that there results apH of greater than 7.0, especially between 7.5 and 8.0. A water-solublephosphate is preferably added to the resulting end product, wherein abuffer action occurs as a result of the third stage of dissociation ofthe orthophosphoric acid. This satisfies the requirement that a pH valueof greater than 7 is maintained.

Although the known process described above admittedly leads toadvantageous uses in individual cases, subsequent scientific tests haveshown that the chemical designations connected with it are notapplicable and, further, improvements would be desirable. With respectto the incorrect formulas, reference is had to M. Rimpler, W. Regment,D. Pacik, "Balneozoon und Hydroxan, Die Anwendung non halogenhaltigenSauerstoffkomplexen fur die Balneologie und den Schwimmbadbereich[Balneo-organisms and Hydroxan, The Use of Halogen-containing OxygenComplexes in Balneology and Swimming Pools]", Forum Stadte-Hygiene 43(1992) Sept./Oct., pages 226-230. It is shown in this article thatchlorine dioxide formed according to the known process is transferred inthe presence of chlorite ions to a charge-transfer complex of theformula Cl₂ O₄ ⁻ which converts to the tetrachlorodecaoxide anion in thealkaline range by means of oxygen. This anion can also be formed fromchlorine dioxide through the action of an oxidizing agent such ashydrogen peroxide. The disadvantage of the products obtained by means ofthe known methods consists in that they all contain chlorite which isdisadvantageously liberated when used, for example, for the treatment ofdrinking water. In this connection, it must be considered particularlyin regard to the treatment of drinking water that legally prescribedlimits for chlorite may not be exceeded. The currently applicablemaximum value is 0.2 mg chlorite/l.

Oxoferin® is a known activated oxygen which is stabilized in alkalinemedium and embedded in a matrix of chlorite ions. The stabilizedactivated oxygen is in the form of a solution. A medication containingthis activated oxygen can be advantageously used for the treatment ofskin damage or for wound healing disorders. Its production is describedin EP-A-0 093 875.

In the Olin system, chlorine bleach and a chlorite solution are reactedat a pH of 3.5 to 4. Sulfuric acid is used to adjust the pH. This systemis commercially available as Model 350 Dioxolin. This process is carriedout in a single mixing process, which leads to uncontrolled processesand complex mixtures. It has the further disadvantage that no buffer isprovided by the sulfuric acid.

As was first described in W. J. Masschelein, Trib. Eau 42 (542); 1990,pages 49-52, chlorine dioxide has a toxic effect on Legionella. Thechlorine dioxide used for technical purposes in this reference wasobtained from chlorite and acetic anhydride. After consumption of thestrong oxidizing agent chlorine dioxide, a mixture of this kind, due tothe acetate carbon body contained therein, is a nutritional base forother undesirable microorganisms especially in drinking water systems.This fact therefore militates against the use of an aqueous chlorinedioxide mixture of this kind in the foodstuff and drinking waterdomains, especially since the addition of organics to drinking water hasmeanwhile been prohibited in many countries (e.g., in the German FederalRepublic (TVO)).

Aside from the above-described processes for chlorine dioxide productionthrough oxidation or disproportionation of chlorite, chlorine dioxidecan also be obtained by reduction of chlorates. A process of this typeis the Mathieson process or sulfur dioxide process. This is acounterflow process in which a solution of sodium chlorate is mixed withsulfuric acid at the head of a reaction vessel and an air-sulfur dioxidemixture is blown in at the bottom. An air-chlorine dioxide mixture canbe removed from the head of this reactor. This mixture also containsproportions of chlorine.

In order to reduce any chlorine that is formed, a surplus of sulfurdioxide is used in the process. The addition of chloride ions alsoincreases the yield of chlorine dioxide. A process of this kind isdisclosed, e.g., in WO 90/05698.

The Solvay process or methanol process uses methanol for the reductionof the chlorate. Since the reaction speed of this process is lower thanthat of the Mathieson process, the process must be carried out at ahigher temperature. A process of this kind is described, e.g., in EP 0357 198.

Chlorate can also be reduced to chlorine dioxide by chloride. Theresulting chlorine dioxide is always contaminated with chlorine gas. Ifthis contamination is undesirable, the chlorine dioxide is absorbed byan aqueous solution and thus separated from the chlorine. A process ofthis kind is described in EP 0 106 503.

OBJECT AND SUMMARY OF THE INVENTION

The primary object of the present invention is to further develop theprocess described above in such a way that aqueous chlorite solutionsare converted to a desired end concentration of chlorine dioxide in theproduct of the process through a simple and dependable management of theprocess by means of a suitable selection of the concentration of startermaterials. In so doing, unwanted chlorite is extensively eliminated sothat the level of chlorite per liter can be maintained safely below themaximum prescribed by currently applicable drinking water regulations(0.2 mg of chlorite per liter). Contamination by harmful organics isalso eliminated.

According to the invention, this object is met in that an acidic aqueoussolution A is produced which has a pH of about 5 or less and containsthe oxo acids and/or oxo acid anions, and the acidic aqueous solution Ais mixed with an aqueous chlorite solution B to form chlorine dioxide,wherein a pH of less than 6.95 is adjusted in the reaction mixture, thispH value being stabilized by an incorporated buffering system. Aqueouschlorine dioxide solutions are particularly stable in this range.

For the purpose of the invention, "oxo acids and/or oxo acid anions"denotes a system of species in protolytic equilibrium which are derivedfrom oxo acids (elemental oxygen acids) whose redox potential (oxidationpotential) is suitable for the oxidation of chlorite to chlorinedioxide. The standard redox potential for gaseous ClO₂ is 1.15 V and0.95 V for ClO₂ dissolved in water. The utilized oxo acid must thereforehave a redox potential in this order of magnitude or greater under thereaction conditions. For the definition of redox potential, reference ishad to Rompp Chemie-Lexikon, Franckh'sche Verlagshandlung, Stuttgart,8th Edition, 1985, page 3522. Accordingly, oxo acids will be understoodhereinafter also to include oxo acid anions in protolytic equilibriumunless otherwise noted. Suitable examples of oxo acids includehypochlorous acid, permonosulfuric acid (Caro's acid), perdisulfuricacid, permanganic acid, and other acids with sufficient redox potential.Hypochlorous acid and permonosulfuric acid are preferred.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention will be described more fully hereinafter using the exampleof hypochlorous acid. However, all remarks pertain equally to other oxoacids within the meaning of the invention whenever applicable.

The essential distinguishing feature of the invention consists in theproduction of an acidic aqueous solution of hypochlorous acid with a pHof about 5 or less. The pH of the acidic aqueous solution A ispreferably adjusted to about 1 to about 5, particularly from 1.5 to 3.5.This acidic aqueous solution A is subsequently mixed with an aqueouschlorite solution B. The solution A must be sufficiently acid so that apH of less than 6.95 results in the reaction mixture. The pH of lessthan 6.95 must be stabilized by an incorporated buffer system. Theincorporation of the above-mentioned buffer system serves primarily toprevent the pH from rising to values of greater than 6.95. This risk ispresent, for example, when using lime-containing tap water. That is, ifthe reaction system is changed to the neutral or even alkaline range,the disadvantages and unwanted consequences described above will occur.Thus, the oxidizing power of the hypochlorous acid is less pronounced inthe alkaline range and there is a tendency, moreover, towarddisproportionation reactions, wherein chlorate can also form, amongothers. On the other hand, the pH of the reaction mixture must beprevented from dropping too far. The specified lower limit of the pHvalue is approximately 2. Below this value, chlorate formation can occuraccording to the following equation:

    4ClO.sub.2.sup.- +2H.sup.+→ Cl.sup.- +2ClO.sub.2 +ClO.sub.3.sup.- +H.sub.2 O

In order to maintain this pH range, it may be necessary in individualcases to use two different buffer systems.

Modifications are possible in the incorporation of the buffering system.For example, an acidified hypochlorite solution can be mixed with anaqueous chlorite solution while simultaneously incorporating the buffersystem. Alternatively, and preferably, the acidic aqueous solution Aincorporates a buffer system. The buffer system is preferably a weakacid. Weak acids within the meaning of the invention are characterizedby a pK₅ value in the region of approximately 1 to 9. Weak acids withinthe meaning of the invention are also multiproton acids if their pK₅values fall within the above-indicated range.

The acidic aqueous solution A can already be sufficiently acid itself,due to the utilized oxo acid, to dispense with further addition of acid.If the utilized oxo acid is too weak or if the oxo acid anions are usedto start, it is necessary to add an external acid for acidification. Theinvention is not subject to any special limitations as regards thechoice of acid for acidification. The acids may be strong or weak. Thefollowing acids are mentioned by way of example: hydrochloric acid,sulfuric acid, acetic acid, phosphoric acid or suitable Lewis acids.

The use of weak acids is particularly advantageous, since theysimultaneously fulfill the function of a buffer system in the reactionsystem after partial neutralization through the alkaline chloritesolution B. Orthophosphoric acid is particularly preferred. By suitableselection of the amount of phosphoric acid, a mixture of primary andsecondary phosphate is present in the reaction mixture which buffers inthe pH range of around 6.92 or less.

It is particularly advantageous within the scope of the invention whenan aqueous solution of hypochlorous acid is produced by acidifying anaqueous solution of an alkaline hypochlorite or alkaline-earthhypochlorite, for example. Similarly, a solution of permonosulfuric acidis advantageously obtained by acidification of an aqueous solution ofalkali salts and/or alkaline-earth salts of permonosulfuric acid. Also,in this connection, phosphoric acid produces advantageous resultsbecause it is a medium-strong acid with a pK₅ value of 1.96 in its firstdissociation stage. Especially within the acidic aqueous solution A,this stage ensures the buffering of the latter in the pH range around 2.When mixed with the alkaline aqueous chlorite solution, the phosphoricacid causes the buffering, in accordance with the invention, at a valuebelow 6.95 due to the suitable position of its second dissociationconstant. If another acid is used, it may be necessary to include anadditional buffer system suitable for stabilizing the pH occurring inthe reaction mixture at below 6.95. Suitable buffer systems aredescribed, for example, in D. D. Perrin and B. Dempsey, "Buffers for pHand Metal Ion Control", Chapman and Hall Ltd., London, first edition,1974.

The person skilled in the art is not subject to any importantrestrictions as regards the "chlorite" solution discussed within theframework of the invention. It is preferably an alkaline chlorite and/oralkaline-earth chlorite, especially sodium chlorite, potassium chloriteand calcium chlorite.

Reaction is referred to expressly within the framework of the invention.By this is meant that an extensively quantitative stoichiometricreaction of chlorite with oxo acid is carried out, which is ensured at amolar ratio of (1.1 to 0.9):1, preferably 1:1, in relation to redoxequivalents. By a unit related to redox equivalents is meant thehypothetical fraction of the oxo acid which is capable of taking on anelectron. The reaction of chlorite with hypochlorous acid is accordinglycarried out in the quantitative framework of (1.8 to 2.2):1, preferably2:1. In this range, acceptable results are achieved in connection withdrinking water and bathing water in comparison with the conventionalprocess of the prior art. In particular, it would not be prejudicial tothe objective of the process if the amount of hypochlorous acid wereslightly in excess of the exact stoichiometric ratio. In order to meetthe objective, a solution A whose concentration of hypochlorous acid isexactly known is advantageously added to the respective reactor forreaction with the chlorite solution. In particular, this makes itpossible to determine the concentration of hypochlorous acid withoutdelay by measuring the redox potential. Voltage values are determined inmV by means of a redox measuring system which immediately provides thepresent concentration of hypochlorous acid with the aid of the Nernstequation. The readout value in mV corresponds to a fixed concentration.This concentration is in turn used within the framework of the inventionto suitably balance the amounts or concentrations of solution A andsolution B, e.g., in order to be able to maintain the exactly adapted ordesired quantity of hypochlorous acid at a given flow of the aqueouschlorite solution into the reactor system.

The process according to the invention can be carried out in anyreactor. These can be reactors for batchwise (intermittent) operation orcontinuous operation. Homogeneous, stationary stirring-tank reactors,stirring-tank reactors in a cascade arrangement or reaction tubes orflow tubes are suitable. The latter enable advantageous continuousoperation. However, it must be ensured, particularly in flow tubes, thatturbulent conditions are maintained therein, wherein the Reynolds numbermust be above 2,300. With regard to the Reynolds Number, reference ishad to Rompp Chemielexikon, 9th Edition, Vol. 5, 1992, pages 3861-3862.Turbulent conditions can easily be achieved therein by installingturbulence-generating elements such as Raschig rings in particular.Further, it is self-evident that a sufficiently long reaction time mustbe observed for the reaction in the reaction mixture. In order to ensurethis, a Bodenstein number from 0 to approximately 500 can be specified.The Bodenstein number within the reaction system is particularlypreferably between 5 and 40. Details concerning the Bodenstein numberare given in E. Fitzer, W. Fritz, "Technische Chemie, eine Einfuhrung indie Chemische Reaktionstechnik [Technical Chemistry, An introduction toChemical Reaction Systems]", 2nd edition, Springer-Verlag 1982, pages343 to 352, especially page 346.

With respect to the use of the chlorine dioxide solution obtainedaccording to the invention for treatment of drinking water, it isadvantageous to add a hypochlorite solution to this chlorine dioxidesolution, in particular a sodium hypochlorite solution, for the renewedformation of hypochlorous acid. In this way, the possible formation ofchlorite ions is suppressed or excluded when applied. By addinghypochlorous acid, chlorite formed by redox reaction is immediatelyconverted into chlorine dioxide again, ensuring a long-lasting effect.The maximum achievable chlorite concentration can be limited by theinitially selected chlorine dioxide concentration, so that the maximumpermissible chlorite concentration for drinking water can be adhered toin a simple manner.

The combination of hypochlorous acid with chlorine dioxide solutionleads to a synergistic effect resulting in an optimizing of the safe useof the product of the process and efficiency for guaranteeing drinkingwater hygiene. In this connection, the invention makes deliberate use ofthe advantageous bactericidal dynamics achieved by the synergisticaction of chlorine dioxide and hypochlorous acid in killing bacteriaWhile the chlorine dioxide is clearly better for attacking and damagingthe lipid component of the bacterial membrane, the hypochlorous acidreinforces the results in a lasting manner. This offers the specialadvantage of effective elimination of Legionella Pneumophila which isresponsible for Legionnaires' disease.

BRIEF DESCRIPTION OF THE DRAWING

An apparatus for carrying out the process according to the inventionwhich has special advantages is described by way of example withreference to the accompanying FIG. 1. FIG. 1 describes an apparatus thathas a flow tube reactor with a vertical flow from top to bottom which isfilled with turbulence-generating elements. In particular, the followingreference numbers are used in a preferred construction: 1=water supply,2=metering of phosphoric acid, 3=metering of chlorine bleach, 4=redoxelectrode, 5=metering of chlorite solution, 6=flow tube reactor withRaschig rings, 7=metering of chlorine bleach, and 8=supply vessel.

The present invention is linked with many advantages. A stable, bufferedaqueous chlorine dioxide solution can be produced in a simple manner,for example, using a flow tube reactor. For this purpose, commerciallyavailable alkaline hypochlorites and alkaline chlorites can be used tostart. The solution of the alkaline chlorite is advantageously acidifiedwith phosphoric acid resulting in the simultaneous introduction of thebuffer system H₂ PO₄ ⁻ /HPO₄ ²⁻ which stabilizes the finished reactionmixture at a pH of less than 6.95. However, other acids can also beused, wherein it may be necessary to add an external buffer system whichbuffers in approximately the same range. A chlorine dioxide solutionwith a surplus of ClO⁻ surplus can be prepared for preventingreformation of chlorites. The use of hydrogen peroxide or otherperoxides with their undesirable effects can be excluded. Further, theabove-mentioned addition of phosphoric acid offers the additionaladvantage that it is a corrosion inhibitor when the product of theprocess is applied in metallic systems. The aqueous chlorine dioxidesolution obtained according to the invention can be used in aparticularly advantageous manner for the disinfection of drinking waterand of water for industrial or business use and for the disinfection ofswimming pool water. A further area of application is in the treatmentof cyanide-containing waste water from electrolytic processes. Thedestruction of cyanide by means of chlorine dioxide leads to the cyanateby way of cyanogen in accordance with the following formula: ##STR1##The resulting chlorite can in turn react, in the presence of transitionmetals, with cyanides to form cyanate and chloride. A chlorine dioxidesolution according to the invention can also destroy cyano complexes,e.g.:

    5[Cu(CN).sub.3 ].sup.2- +7ClO.sub.2 +12.sup.- OH→15CNO.sup.- +7Cl.sup.- +5Cu(OH).sub.2 +H.sub.2 O

The aqueous chlorine dioxide solution which is formed is preferablyadjusted to a pH of about 9 to 10 prior to use for destroying cyanidesand cyano-metal complexes. The formation of hydrogen cyanide is reliablyruled out by this step.

Cyanide detoxification is carried out with the chlorine dioxide solutionaccording to the invention faster and better than when using purechlorine bleach; in this connection, reference is had to Cocheci, V.,Taubert, R., and Martin, A., "Removal of Cyanide from Wastewater", BullStiint. Teh. Inst. Politeh. Timisoara, 1969, 14 (2), pages 497-502. Thechlorine dioxide solution obtained in accordance with the invention canalso be used for reducing CSB/BSB and for breaking up metal complexesfor subsequent precipitation of the metals and removal of the metalsfrom the wastewater by means of ion exchange and sorption processes.

The invention will be explained more fully hereinafter by means ofexamples.

EXAMPLE 1

In a flow tube reactor, 0.08 ml/s of a hypochlorite ion-containingaqueous solution (78.49 g OCl⁻ /l) and 0.56 ml/s of an orthophosphoricacid (145.35 g/l) are introduced through two injection locations locatedopposite one another at a Reynolds Number greater than 2,300 in a volumeflow of 8.33* 10⁻⁵ m³ /s of water. After mixing the two components inthe turbulent aqueous flow, a redox potential (platinum electrode with asilver-silver chloride electrode) of approximately 1,200 mV is measured.The pH of this solution is 2.5. A chlorite-containing aqueous solution(388.08 g ClO⁻ /l) is introduced at 0.043 ml/s into this volume flowthrough an injection location directly preceding a flow reactor. Thereaction mixture then enters the tube reactor and remains therein for aholding time of approximately 32 s. During this time period, thehypochlorite is reacted with the chlorite quantitatively to formchlorine dioxide and chloride.

After the products exit the reactor, 0.318 ml/s of the chlorine bleachmentioned above is injected into the volume flow by means of anadditional injection location. The solution now has a pH of 3.65 and theredox potential is approximately 1.051 mV. This preparation (0.2 g/lchlorine dioxide and 0.3 g/l HOCl) is collected in a supply vessel andcan be dispensed from there into a drinking water system.

EXAMPLE 2

The same steps are taken as in Example 1. However, after the tubereactor, a redox-inactive base is added instead of the chlorine bleach,so that the pH value of the reaction mixture in the supply vessel isbetween 9 and 10. An oxidant solution of this type adjusted in thealkaline range is used in systems in which an alkaline milieu ispreferred, e.g., when cyano complexes are to be destroyed and the heavymetal ions simultaneously precipitated as hydroxide complexes. It isnoted that the chlorine dioxide solution is first adjusted to a high pHbefore use. The production of the chlorine dioxide solution is carriedout, according to the invention, in a buffered, slightly acidic pHresulting in the advantage that the reaction is carried outquantitatively and no formation of chlorate occurs.

While the foregoing description and drawings represent the preferredembodiments of the present invention, it will be obvious to thoseskilled in the art that various changes and modifications may be madetherein without departing from the true spirit and scope of the presentinvention.

What is claimed is:
 1. A process for the production of aqueous chlorinedioxide solutions through oxidation of chlorite with oxo acids and/oroxo acid anions having a suitable redox potential in a buffered aqueousmedium, comprising the steps of:producing an acidic aqueous solution Awhich has a pH of about 5 or less and contains the oxo acids and/or oxoacid anions; and mixing the acidic aqueous solution A with an aqueouschlorite solution B to form chlorine dioxide, wherein a pH of less than6.95 is adjusted in the reaction mixture, said pH value being stabilizedby a buffering system contained therein.
 2. The process according toclaim 1, wherein the pH of the acidic aqueous solution A is adjusted toapproximately 1 to approximately
 5. 3. The process according to claim 1,wherein an aqueous solution of alkaline salts and/or alkaline-earthsalts of chlorous acid are/is used as solution B.
 4. The processaccording to claim 1, wherein the concentration of the system of oxoacids and/or oxo acid anions in the acidic aqueous solution A isdetermined by measuring the redox potential and the quantities ofsolution A and solution B are correspondingly balanced.
 5. The processaccording to claim 1, wherein hypochlorous acid/hypochlorite and/orpermonosulfuric acid/permonosulfate are used as oxo acids and/or as oxoacid anions.
 6. The process according to claim 5, wherein the acidicaqueous solution A is obtained by acidifying a solution of alkalinesalts and/or alkaline-earth salts of hypochlorous acid and/or ofpermonosulfuric acid.
 7. The process according to claim 1, wherein thechlorite is reacted with the system of oxo acids and/or oxo acid anionsin a molar ratio, with respect to redox equivalents, of (1.1 to 0.9):1.8. The process of claim 7, wherein the molar ratio is approximately 1:1.9. The process according to claim 1, wherein a Bodenstein number from 0to approximately 500, is maintained in the reactor for extensiveoxidation of chlorite with the system of oxo acids and/or oxo acidanions.
 10. The process of claim 9, wherein the Bodenstein number isbetween approximately 5 and
 40. 11. The process according to claim 1,wherein the reaction mixture for oxidation of the chlorite is carriedout with a continuous-operation reaction reactor.
 12. The processaccording to claim 11, wherein a flow tube is used as reaction reactor.13. The process according to claim 1, wherein the process is carried outin a reaction reactor in which a Reynolds number greater than 2,300 isadjusted.
 14. The process according to claim 13, whereinturbulence-generating elements are installed in the flow tube.
 15. Theprocess according to claim 1, wherein an aqueous hypochlorite solution,is additionally added to the formed aqueous chlorine dioxide solution inorder to form hypochlorous acid.
 16. The process of claim 15, whereinthe added solution is a sodium hypochlorite solution.
 17. The processaccording to claim 1, wherein the buffering system is incorporated intothe acidic aqueous solution A.
 18. The process according to claim 17,wherein a weak acid with a suitable pK₅ value is incorporated in theacidic aqueous solution A as a buffering system.
 19. The processaccording to claim 18, wherein the weak acid is added to the aqueoussolution A for acidifying and for incorporating the buffering systemsimultaneously.
 20. The process according to claim 18, whereinorthophosphoric acid is used as weak acid.